Chemical sensing device

ABSTRACT

A chemical sensing system includes a substrate material, a detector capable of indicating a presence of a target compound, gas, or vapor, and a heater for rapidly releasing compounds, gases and vapors from the substrate material. The substrate material acts to concentrate the compounds, gases, and vapors from a sample area for improved detection by the detector.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.61/862,250 filed on Aug. 5, 2013, which is hereby incorporated byreference in its entirety.

GOVERNMENT INTEREST

This invention was made with Government support under Contract No.W911S6-10-C-0011 awarded by the U.S. Army. This invention was also madewith Government support under Contract No. D11PC20126 awarded by theU.S. Department of the Interior, NBC Acquisition Services Directorate.The Government has certain rights in this invention.

SUMMARY

The ability to detect trace amounts of volatile organic compounds isoften required for chemical sensors such as warfare gas stimulants,explosives, and volatile organic compounds in mouth breath, etc.

Embodiments are directed to preconcentrators including a cartridgehaving a hollow body sized to contain a substrate enclosed within thecartridge. In some embodiments, the substrate may be metal fiber, wovenmetal fibers, non-woven metal fibers, porous metal, sheet metal, metalcoated glass, metal coated plastic, metal coated ceramic, carbonaceousmaterial, graphite, charcoal, activated carbon, activated carbon cloth,and combinations thereof. In certain embodiments, the substrate may haveresistivity of about 10⁵ ohm-meters (Ω·m) to about 10⁻⁷ Ω·m, magneticpermeability of greater than about 1×10⁻⁴ H/m, relative permeability ofgreater than 100, or combinations thereof. In particular embodiments,the substrate may have an electrical resistivity of greater than 10³Ω·m. In certain embodiments, the cartridge may include at least a firstreversibly sealable opening on one side of the cartridge and at least asecond reversibly sealable opening on the opposite side of thecartridge.

Other embodiments are directed to a method for detecting an chemicalincluding the steps of collecting particles, gases, and vapors in apreconcentrator having a substrate having resistivity of about 10⁵ohm-meters Ω·m) to about 10⁻⁷ Ω·m; heating the substrate to release theparticles, gases, and vapors; and detecting the chemical in theparticles, gases, and vapors. In some embodiments, the substrate mayhave magnetic permeability of greater than about 1×10⁻⁴ H/m, relativepermeability of greater than 100, or combinations thereof. In certainembodiments, the heating may be inductive heating, and in someembodiments, inductive heating is carried out at a frequency of about100 kHz to about 10 MHz. In particular embodiments, heating may becarried out to about 120° C. to about 300° C.

Further embodiments are directed to a sample collector including asample collector housing having a preconcentrator holder sized toreversibly receive a preconcentrator; and an air suction pump operablyconnected to the sample collector housing and configured to produce airflow through the preconcentrator. In some embodiments, the samplecollector may further include a pulsed air nozzle connected to thesample collector housing, and in certain embodiments, an air compressormay be operably connected to the sample collector housing and configuredto expel air from the pulsed air nozzle and direct the expelled airtoward a sample collection area. In various embodiments, the air suctionpump may provide a flow of 1 m³/min to 10 m³/min. In certainembodiments, the preconcentrator may include a substrate havingresistivity of about 10⁵ ohm-meters (Ω·m) to about 10⁻⁷ Ω·m

Additional embodiments are directed to a system including a samplecollector having a sample collector housing having a preconcentratorholder sized to reversibly receive a preconcentrator; and a detectorincluding a detector housing having an detector access port sized toreversibly receive the preconcentrator; an induction heater containedwithin the detector housing, the induction heater configured to heat thepreconcentrator; and a sensing system operably connected to the accessport and positioned to receive particles, gases, and vapors from thepreconcentrator when the preconcentrator is received by the detector. Insome embodiments, the detector my further include an air suction pumpoperably connected to the access port and configured to produce air flowthrough the preconcentrator, and in some embodiments, the air suctionpump may provide a flow of 1 m³/min to 10 m³/min. In certainembodiments, the preconcentrator may include a substrate havingresistivity of about 10⁵ ohm-meters (Ω·m) to about 10⁻⁷ Ω·m. In variousembodiments, the preconcentrator may include a cartridge and a substratehaving a resistivity of about 10⁵ ohm-meters (Ω·m) to about 10⁻⁷ Ω·menclosed within the cartridge. in some embodiments, the detector mayinclude a temperature feedback that limits the temperature to about 120°C. to about 300° C. In particular embodiments, the detector furthercomprises a compressor operably connected to the detector access portand configured to generate a differential pressure across thepreconcentrator when the preconcentrator is received by the detector.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 represents a general flow diagram of operating a sensing systemaccording to an embodiment.

FIG. 2 depicts a general representation of a chemical sensing systemaccording to an embodiment.

FIG. 3 depicts a sketch of a sample collector according to anembodiment.

FIG. 4 depicts a chemical sensing system having an induction heateraccording to an embodiment.

FIG. 5 depicts a general representation of an induction heating system.

FIG. 6 depicts a miniature trace explosives trace preconcentrator deviceaccording to an embodiment.

FIG. 7 shows MS data for TNT vapors flash extraction afterpreconcentration in dry ambient. Initial TNT vapor flow was belowdetection limit (<1000 counts).

FIG. 8 shows MS data for TNT vapors flash extraction afterpreconcentration in wet ambient.

FIG. 9 shows with preconcentrator substrates with TSI coating, othercoating and uncoated metal mesh were exposed to TNT vapors for 30, 60,90 and 120 minutes without air circulation. TNT was extracted with asolvent and measured by GC/μECD.

FIG. 10 shows sequence of TNT vapor preconcentration and pulsed vaporrelease. Preconcentrator coating shows no degradation after heating to250° C. for a number of times (up to 25).

FIG. 11 IMS spectra of laboratory air according to an embodiment.

FIG. 12 shows IMS spectra of DNT vapors continuously injected into IMSdetector from a syringe according to an embodiment. The showed spectrawere taken with interval of 1 sec.

FIG. 13 shows IMS spectra of nitroglycerine vapors passed through thepreconcentrator and injected into IMS detector.

FIG. 14 shows IMS spectra of previously collected DNT vapor releasedwithin 1.8 sec of heating of preconcentrator with various release flowrates of 50, 75, 100 and 120 ml/min.

DETAILED DESCRIPTION

Embodiments of the invention are directed to systems and methods forchemical detecting and various components of the systems. Someembodiments are directed to preconcentrators and the various componentsof a preconcentrator collector system for collecting and concentratingchemicals from a collection area. Other embodiments are directed todevices including sensors and other components capable of releasing thechemicals collected from the collection area and sensing particularchemicals from the collected sample. Still other embodiments using thepreconcentrators, sample collectors, and sensors, detectors and otherdevices associated with these systems.

In various embodiments, the preconcentrator may be a hollow body sizedto contain a substrate capable of reversably bonding to various chemicalspecies. The tubular hollow body may have at least a first reversiblysealable opening on one side of the hollow body and at least a secondreversibly sealable opening on the opposite side of the hollow body. Forexample, in some embodiments, the preconcentrator may be cylindricalcartridge with circular openings on each end of the cylinder. In otherembodiments, the preconcentrator may be disk shaped having concave diskshaped ends connected by a broad cylindrical body providing asubstantially obround hollow body. Openings may be provided on anysurface of the disk shaped body.

The reversible sealable openings on the preconcentrator may be createdby any means. For example, in certain embodiments, the reversible sealmay be removable caps, stoppers, corks, plastic films, or combinationsthereof. In other embodiments, the reversible seals may be integral tothe cartridge. For example, the openings may be sealed using hingedcovers or slide covers that can be moved to allow access to the internalhollow body of the cartridge during use and then resealed after thesample has been obtained. In still other embodiments, the openings maybe sealed using both integral hinged or slide covers and removable capsor plastic films.

Certain embodiments are directed to preconcentrators having a substratethat is capable of reversably bonding to various chemical species, andin certain embodiments, the substrate may be capable of releasing boundchemical species when heated or placed in a magnetic field. In someembodiments, the substrate may a resistivity of about 10³ ohm-meters(Ω·m) to about 10⁻⁹ Ω·m, about 10⁵ ohm-meters (Ω·m) to about 10⁻⁷ Ω·m,about 10⁴ ohm-meters (Ω·m) to about 10⁻⁶ Ω·m, about 10³ ohm-meters (Ω·m)to about 10⁻⁵ Ω·m, or any range or individual value encompassed by theseexample ranges. In some embodiments, the substrate may have a magneticpermeability (μ) of greater than about 1×10⁻⁴ H/m or, in certainembodiments, about 1×10⁻⁵ H/m to about about 10 H/m, about 1×10⁻⁴ H/m toabout 1 H/m, about 1×10⁻³ H/m to about 0.1 H/m, or any range orindividual value encompassed by these example ranges. In someembodiments, the substrate may have a relative permeability of greaterthan 100, or, in particular embodiments, the relative permeability maybe about 75 to about 500, about 100 to about 400, about 150 to about 250or any range or individual value encompassed by these example ranges. Ofcourse, in various embodiments, the substrate may have any combinationof resistivity, magnetic permeability, and relative permeability inwhich each range is encompassed by one or more of the example rangesdescribed above. The substrate of such embodiments may be composed of avariety of materials including, for example, metal fiber, woven metalfibers, non-woven metal fibers, porous metal, sheet metal, metal coatedglass, metal coated plastic, metal coated ceramic, carbonaceousmaterial, graphite, charcoal, activated carbon, activated carbon cloth,and combinations thereof. In some embodiments, the substrate may beporous to enable the flow of air through the preconcentrator.

Examples of substrates may include, but are not limited to, steel wool,nickel foam, ZnFe₂O₄ nanorods, iron nanoparticles/glass wool, Co-ferriteaerogel, magnetic stainless steel wool and the like. The physicalproperties of these substrates are described in Table 1.

TABLE 1 Specific Surface Heating Pressure Substrate μ Heat Area RatesDrop material (H/m) (kg/kJ ° K) (m²/g) (° C./s) (PSI) Steel Wool 8.75E−40.49 0.0075 50 (#3) Steel Wool 8.75E−4 0.49 0.0759 76 0.38 (#0000)Nickel Foam 1.25E−4 0.54 0.0026 60 0.08 ZnFe₂O₄ 4.01E−4 — 13.6 —Nanorods COTS Ferrite 5.03E−5 1.05 0.000949 45.4 0.79 rod (NiZn) Iron ~10.67 0.7 17.5 Nanoparticles/ Glass Wool Co-Ferrite 3.27E−4 — 350 — 1.39aerogel* 434 Magnetic 8.75E−4 0.49 0.0075 52 0.37 Stainless Steel wool(#3)In Table 1, magnetic permeability (μ) defines the response of materialto magnetic field, specific heat defines the material's ability to beheated, surface area describes the exposed surface area of the materialthat is capable of binding to a chemical species, where a higher surfacearea means higher density of surface binding sites, heating ratedescribes the rate at which the substrate can be heated, and pressuredrop describes the maximize air flow required to increase sample volume.In particular embodiments, the substrate may be steel wool.

In some embodiments, the preconcentrator may include a coating on thesubstrate described herein. The coating in such embodiments may be anycoating that improves either bonding of chemical species to thesubstrate, release of the bound chemical species, or combinationsthereof. In certain embodiments, the coating may be an organic coating.In some embodiments, the coating may generally increase the affinity ofthe substrate for various chemical species. In other embodiments, thecoating may be chemically selective allowing the coated substrate tohave an increased affinity for a specific target species or a particularclass or group of target species. For example, in some embodiments, thecoating may provide higher affinity for target chemical species, whilereducing the substrates affinity for common background chemicals, suchas water vapor, cigarette smoke, exhaust fumes, gasoline fumes, dust,pollen, and the like or combinations thereof. In certain embodiments,the coating may increase the affinity of the substrate for chemicalspecies including, but not limited to, explosives, chemical warfareagents, and toxic industrial compounds.

In particular embodiments, the coating may provide discriminationbetween water and polar analytes. Thus, the coating may have an affinityfor polar chemical species while repulsing water and non-polar chemicalspecies, such as water vapor, cigarette smoke, exhaust fumes, gasolinefumes, dust, pollen, and the like or combinations thereof. In someembodiments, this discrimination can be achieved by combining polar andnon-polar functional groups into the coating, and in other embodiments,different coating materials having polar or non-polar functionality canbe combined and coated onto the substrate. Including both polar andnon-polar functionality in the coating may allow the non-polar portionto reject water and non-polar interferents, while the polar portionadsorbs the polar chemical species. In this manner, the spurious signalsdue to water and interferents can be eliminated, while simultaneouslyenhancing the signals due to the polar molecules. Embodiments, are notlimited to particular polar or non-polar functional groups. For example,in some embodiments, the polar functional groups may include amide(—C(O)NH₂), C₁-C₁₀ alkyl amide, carboxylic acid (—COOH), C₁-C₁₀ alkylcarboxylic acid, hydroxyl (—OH), C₁-C₁₀ alkyl hydroxyl, C₁-C₁₀ alkyoxy,aldehyde (—C(O)H), C₁-C₁₀ alkyl aldehyde, ketone (—C(O)CH₃), C₁-C₁₀alkyl ketone, amine (—NH₂), C₁-C₁₀ alkyl amine, epoxide, carbonyl group,and combinations thereof. In various embodiments, the non-polarfunctional groups incorporated into the coatings described above may beC₁-C₁₀ alkyl, C₂-C₁₀ alkene, C₂-C₁₀ alkyne, C₆-C₁₆ arene, halide (Br, F,Cl), C₁-C₁₀ alkyl halide, cycloalkyl, and combinations thereof.

In certain embodiments, the coatings may be a polymer having aromatic,or aliphatic backbone, and in certain embodiments, the backbone maycontain benzene, toluene, xylene, cyclohexane, dimethylcyclohexane,ethylcyclohexane, and combinations thereof. In particular embodiments,the coating may be composed of functionalized xylene. For example, thecoating may be a copolymer of 4-hydroxy[2.2]paracyclophane and4-perfluoroalkyl-carbonly[2.2]paracyclophane, in which the —OH groups onthe surface allow for the attachment of polar molecules while theTeflon-like fluorine chain acts as a hydrophobic barrier to waterstabilization on the surface.

The coatings of various embodiments are generally thinly applied to thesubstrate. For example, in certain embodiments, the coating may have athickness of about 200 nm. In other embodiments, the coating may have athickness of about 100 nm to about 500 nm. The coating may be providedon any surface of the substrate, and in certain embodiments, thesubstrate may be substantially coated on all surfaces. For example, thecoating may cover from about 50% to about 99% of the total surface areaof the substrate, or in some embodiments, the coating may cover about75% to about 98%, about 80% to about 97%, about 85% to about 95% of thetotal surface area of the substrate or any individual value or rangeencompassed by these values.

The coating may be applied by any method that provides for a conformalcoating over the various features of the substrate. In an embodiment,the coating may be applied by chemical vapor deposition (CVD).Vapor-based coating enables coating a variety of substrate architecturesranging from planar surfaces such as metal and silicon to interwovenscaffolds such as steel wool. Monomers having diverse functionalization,such as, for example, functionalized monomers of highly adhesivep-xylene, may be applied by CVD, and a resultant copolymerization leadsto uniform multi-functional surfaces, and also modulates surfaceproperties such as composition, hydrophobicity, and surface charge. Thisallows for conformal coating of surfaces instead of the spin-coating orwet deposition methods that are common in the field. Conformal coatingsare important to micro-machined sensors and pre-concentrators due togaps that may form in the coating due to surface tension in the spincast film. In some embodiments, the coating may be applied by othertechniques known in the art, such as layer-by-layer assembly, one sidedplasma enhanced chemical vapor deposition, and one-sidedphotopolymerization.

The preconcentrators described herein can be used in a variety ofsystems for sensing chemical species. For example, in some embodiments,the preconcentrators may be incorporated into larger sensing systems. Insome embodiments, the sensing systems may include a separate samplecollector and detector. FIG. 1 is a flow chart describing example of aprocess by which a system including separate sample collection followedby detection. In such embodiments, sample collection S1 may be carriedout by drawing air into a preconcentrator such as the preconcentratorcartridge described above, and various chemical species and other vaporsmay become associated with the substrate in the preconcentrator. In someembodiments, after sample collection, the preconcentrator cartridge maybe sealed. The preconcentrator cartridge can then be transported S2 to alocation that includes a detector. In some embodiments, thepreconcentrator cartridge may be taken to the detector directlyfollowing sample collection. For example, the preconcentrator may bepart of a sample collector and the sample collector may be part of atransportable and movable system that can be carried in a backpack orshoulder carrier, rolled on castors or a mobile cart, or otherwisetransported with the user, so that sample collection and transport tothe detector can occur simultaneously. In other embodiments, thedetector may be maintained at a fixed position and the user maytransport preconcentrator to the detector or have the detectortransported to the preconcentrator. The preconcentrator may then beheated S3 to release the chemical species and other vapors that wereassociated with the substrate during sample collection and the chemicalspecies and vapors may be released into the detector. In someembodiments, heating and release into the detector may occur in thedetector. For example, the detector may be equipped with an inductionheater designed to surround the preconcentrator and means for directingair flow through the preconcentrator and into the detector. In suchembodiments, chemical species and vapors may be released from thepreconcentrator substrate and simultaneously directed into the detector.In other embodiments, the heating unit may be separate from thedetector. The detector may be utilized to detect the chemical species S4released into the detector.

The preconcentrator includes all of the components and physicalproperties described above. In some embodiments, the preconcentrator mayinclude a hollow cartridge that encapsulates the substrate and may beconstructed from various materials such as, for example glass, quartz,Teflon, plastic, aluminum, and the like and combinations thereof. Thepreconcentrator may include a high surface-area substrate. As shown inthe detail of FIG. 4, in some embodiments, the coated substrate mayinclude a porous substrate material 26 with a conformal, stable,chemically selective surface treatment, or coating 28, configured tohave an affinity for the target substrate or substrates. In otherembodiments, the substrate may be uncoated.

The preconcentrator cartridge in FIG. 2 may include an inlet 18 andoutlet 19 that may be reversible sealable openings. The reversiblesealable openings on the preconcentrator may be created by any means.For example, in certain embodiments, the reversible seal may beremovable caps, stoppers, corks, plastic films, or combinations thereof.In other embodiments, the reversible seals may be integral to thecartridge. For example, the openings may be sealed using hinged coversor slide covers that can be moved to allow access to the internal hollowbody of the cartridge during use and then resealed after the sample hasbeen obtained. In still other embodiments, the openings may be sealedusing both integral hinged or slide covers and removable caps, plasticfilms, or stoppers. The stoppers may be constructed of rubber orplastic. To remove the contents of the preconcentrator, the stopper maybe pinched with a hypodermic needle.

Various embodiments include a sample collection system including asample collector 31 as illustrated in FIG. 3. In some embodiments, thepreconcentrator may be reversibly attached to the sample collector, suchthat a preconcentrator can be inserted into the sample collector, asample may be collected, and the preconcentrator may be removed from thesample collector and inserted into a detector device. In otherembodiments, the preconcentrator may be integrated into the samplecollector as part of a larger detector system, and in certainembodiments, this system can be transportable and movable or can becarried in a backpack or shoulder pack.

In various embodiments, the sample collector 31 may include a housing34. In some embodiments, the housing may include an integratedpreconcentrator holder sized to receive the preconcentrator and hold theperconcentrator during sample collecting. The holder may be equippedwith one or more reversible fasteners. For example, the preconcentratoror the cartridge may include grooves that reversible interlock withgrooves in the preconcentrator holder by twisting or screwing thepreconcentrator into the holder. In other embodiments, thepreconcentrator or the cartridge may include one or more ridges thatinterconnect with ridges in the preconcentrator holder allowing thepreconcentrator to snap into the preconcentrator holder. In someembodiments, the preconcentrator holder 33 may be attached to thehousing body 34 by means of a flexible tubing or a hose allowing theuser to move the preconcentrator into small spaces. The preconcentratorholder 33 in such embodiments may be attached to the distal end of thetubing or has and may reversibly hold the preconcentrator 14 during theoperation of the preconcentrator using one or more reversible fastenerssuch as those described above. The preconcentrator holder may furtherinclude mechanism for opening the reversibly sealable ends of thepreconcentrator or the cartridge such that when the preconcentrator isin place, the opening inside the preconcentrator holder is openedallowing free flow of air from the preconcentrator into the samplecollector. In other embodiments, the user may remove the reversiblysealable end of the preconcentrator or the cartridge before introducingthe preconcentrator into the preconcentrator holder.

Air may be drawn through the preconcentrator by an air suction pump 36that is operably connected to the preconcetrator holder 33. The airsuction pump 36 may be any type of air pump known in the art including,for example, a diaphragm pump, rotary vane pump, a piston pump, or a fanthe produces air current through the preconcentrator holder andpreconcentrator. In particular embodiments, the air suction pump may bea regenerative air pump. The flow of the air through the preconcentratorallows the analytes and chemical compounds to be trapped inside thepreconcentrator by binding to the coated substrate, and the air flowproduced by the air suction pump 36 can vary among embodiments. Forexample, in some embodiments, the air flow may produce through thepreconcentrator may be 1 m³/min to 10 m³/min or any individual value orrange encompassed by this range.

In some embodiments, the sample collector may also include a pulsed airnozzle 32 connected to the sample collector housing body 34 that expelsair from the sample collector and is positioned to blow air into asample collection area disturbing particles that may have settled onsurfaces in the sample collection area. The pulsed air nozzle may beintegral to the sample collection having an outlet that is on a surfaceof the sample collector, and in some embodiments, the outlet may includemoveable blades or a nozzle that directs the flow of air away from thesample collector. In other embodiments, the pulsed air nozzle mayinclude a flexible hose or tubing that allows the flow of air to bedirected by the user. In some embodiments, the pulsed air nozzleincluding a flexible hose or tubing may be mounted on a tripod. An aircompressor 35 for producing expelled air can be operably connected tothe pulsed air nozzle 32. In some embodiments, a number of pulsed airnozzles and preconcentrator holders may be connected to the same airsuction pump and air compressor allowing for multiple simultaneoussample collections.

In particular embodiments, the housing body may include control devicesand components 37 to control the working of the air suction pump and theair compressor. In particular embodiments, the sample collector, the airsuction pump, and air compressor can be mounted on a compact wheeledcart.

After sample collection, the preconcentrator may be removed from thesample collector, and then the preconcentrator 14 may be reversiblyconnected to a detector through an access port on the detector device.The detector may include a rapid chemical desorber, that may beconfigured as a heat source 30. In an embodiment as represented by FIG.4, the desorber may be configured as a non-contact miniature inductionheater 30. In an embodiment, the indication heater may be batterypowered for portability of the detection system. Alternatively, for adetection system that may be mounted or placed in a more permanentlocation, a plug-in power source may be provided, and may include a plugfor an alternating current outlet, as well as additional appropriatepower conversion components to vary the voltage, amperage, and type ofcurrent, etc.

In order to increase the concentration of target chemical compounds inthe vapor sample analyzed by a trace detection system, the collectedchemical vapor may be released from the substrate in a very short burstto thereby enter the detection device as a more highly concentratedsample. This may be accomplished by a controlled rapid heating of thepreconcentrator 14. In an embodiment, the heating may be non-contactinductive heating that raises the temperature of the substratesubstantially uniformly to a temperature of about 150° C. to about 250°C. in less than about 5 seconds.

In some embodiments, the detector 12 in FIG. 2 may include a heatingelement 30 that facilitates release of the bound analytes from thesubstrate 24. In some embodiments, a compressor may be further attachedto the detector that generates a differential pressure across thepreconcentrator 14. The differential pressure across the preconcentratorprovides flow of vapors released from the preconcentrator substrate 24and is injected into a chemical analyzer 15. Operation of the heatingelement 30 may be synchronized with time, when differential pressureacross the preconcentrator changes, and air with vapors injected intochemical analyzer. The device has means to control the volume of airwith released vapors injected into chemical analyzer. Such control isprovided by control of time, when differential pressure across thepreconcentrator is not equal to zero.

As represented in FIG. 5, an induction heater may include an inductioncoil 40 (also generally represented as 30 in FIG. 4) having a pluralityof turns of an electrically conductive material 42, such as, for examplea copper wire, that form a tunnel-like structure. While thesolenoid-type coil 40 that is shown in FIG. 5 is one illustrativeembodiment having about eight individual coil turns, it should beunderstood that the solenoid-type coil can include any desired number ofindividual coil turns to form a solenoid-type coil having a desiredspecified length. The solenoid type coil 40 has opposite open ends 43and 44, and a hollow portion 45 of a substantially uniform diameter thatextends along the entire length of the coil and is adapted to receivethe component to be heated, which as shown in FIG. 4, may be a samplecollection cartridge 24. The induction heating coil 40 may be providedwith terminals 50, 51 to connect the solenoid-type coils to a highfrequency power source 55 via power leads 56, 57.

The use of such an induction coil 40 may allow for a rapid and accuratemethod of uniformly heating the contents of the preconcentrator to adesired and predetermined temperature. As shown in FIG. 4, a method ofheating may include providing an induction heating device that includesan elongated solenoid-type induction heating coil 30 in close proximityaround the preconcentrator 14. The term “close proximity” is intended torefer to the positioning of the outer surface of the preconcentrator 14in relation to the induction coil 30. Preferably, the distance betweenthe outer surface of the preconcentrator 14 and the coil 30 should besuch that the magnetic field generated by the coil does not melt thepreconcentrator, but that the portion of the preconcentrator to beheated is within the magnetic field generated by the coil to maximizethe induction heating of that portion of the preconcentrator. As such,an air gap may be present between the outer surface of the portion ofthe preconcentrator 14 to be heated and the induction coil. The air gapmust be such that the induction coil does not contact thepreconcentrator. Without limitation, the air gap between thepreconcentrator and the induction coil may be about 0.1 to about 0.5inch.

The induction heating coil may then be provided or energized with asource of high frequency power, such as a radio-frequency power. Thepower supplied to the induction heating coil may be a supply ofalternating current power. The provision of the high frequencyalternating current to the induction coil produces an electromagneticfield 60 (as shown in FIG. 5), within the solenoid-type coil 30, 40. Theelectromagnetic field produces eddy currents in the substrate material26 and, thus, the coating 28 on the substrate is heated. The highfrequency current is provided to the induction coil for a timesufficient to heat the coating material to a desired and predeterminedtemperature to release any bound analyte. The analyte may then be freeto be carried by an airflow 21 into the detector 12.

An induction heater generally may operates at either medium frequency(MF) or radio frequency (R) ranges. The term “R induction” istraditionally used to describe induction generators designed to work inthe frequency range from about 100 kHz up to about 10 MHz, in practicalterms however the frequency range tends to cover about 100 to about 200kHz. The output range typically incorporates about 2.5 to about 40 kW.The term “MF induction” is traditionally used to describe inductiongenerators designed to work in the frequency range from about 1 to about10 kHz. The output range typically incorporates about 50 to about 500kW. Induction heaters operating within the MF ranges are normallyutilized on medium to larger components and applications.

In an embodiment wherein the high surface-area substrate is made out ofmagnetic stainless steel wool having a high magnetic permeability, aninductive heating may be very efficient with minimal power consumption.In such a scenario, the inductive heating may require less than about 10watts to heat about 0.1 gram of substrate to the desired temp. With thepossibility of such low power requirements, the rapid desorber could bepowered by rechargeable batteries, and depending on the battery size andconfiguration, may allow for over 300 current shots on a single charge.The induction heater circuitry may also include built-in over-currentprotection and feedback controls to limit peak substrate temperature.

Some examples of components of the heater circuitry may include: a basicLC tank circuit driven by MISFIT switches; an on-board tunable frequencygenerator (100-400 kHz); an on-board power supply (battery); an on-boardtemperature measurement for temperatures up to about 350° C.; anover-current protection circuit; an over-voltage protection circuit; atemperature feedback to limit temperature to about 250° C.; aself-tuning frequency feedback loop; an activation circuit to synch withexternal trigger or manual switch 60 in FIG. 6; and on-board statuslights, that may include the following as non-limiting examples, a lowbattery indicator 61, a power-on indicator 62, a fault indicator 63 toindicates over-current or abnormal frequency, and a “Heating” indicator64. The protection circuits may provide multiple protections againstabnormal load conditions, and may include, as non-limiting examples:robust output transistors; a shutdown on fault conditions, such as inputcurrent over 4 amps or a frequency that is too high; a “Pecking” with 2second time-out on continuous fault conditions so that, for example, afault may be left indefinitely without damage; protection againstaccidental high coil voltages; and a circuit board such as a printedcircuit board (PCB) designed to accommodate high currents.

In an embodiment, a miniature induction heater for the detection systemmay be powered by a small Lithium-Polymer Battery (11.1V, 325 math), andthe coil voltage may be adjustable from about 20Vp-p (Volts peak topeak) to about 100Vp-p. The feedback system may be configured toregulate coil voltage to accommodate changes in coil and sampleproperties. The heating may be controlled by manual switch or by logicinput, and the coil and sample cartridge may be easy to remove andreplace when needed.

Induction heating of the pre-concentrating chamber allows for highsubstrate heating rates, with low power consumption in a low maintenancedevice. With induction heating fast desorption of the analyte may beachieved as the RF-coil may induce a magnetic field to cause themagnetic substrate to heat rapidly (greater than about ° 80 C/sec), withminimal power usage—low thermal mass and high permeability may use lessthan about 10 Watts per shot of RF power. An induction heater may alsoprovide reduced maintenance costs as the induction process requires nomoving parts or heating meshes/coils that typically require periodicreplacement. In addition, reduced usage costs may also be provided sincethe coated substrates for use in the detection system may be provided aseasily replaceable cartridges. And, as a safety feature, the maximumtemperature may be controlled by choice of substrate material, mountinggeometry, and coating.

The sensing systems and devices described herein can have multiplecomponents, such as one or more preconcentrators, one or more samplecollectors, one or more heating elements, and one or more detectors as apart of a single unit. In some embodiments, the sensing systems mayinclude a preconcentrator, a sample collector, a heating element, and adetector as separate units, preferably on movable carts. In otherembodiments, the sensing systems may include a preconcentrator and asample collector as one unit, and a heating element and a detector aspart of one unit. In additional embodiments, the sensing systems mayinclude a preconcentrator, a sample collector, and a heating element aspart of one unit, and a detector as a separate unit. In furtherembodiments, the sensing systems described herein may include apreconcentrator, a heating element, and a detector. The presentinvention is not to be limited in scope by the specific embodimentsdescribed above. Many modifications of the present invention, inaddition to those specifically recited above would be apparent to thoseskilled in the art in light of the instant disclosure.

This disclosure is not limited to the particular systems, devices andmethods described, as these may vary. The terminology used in thedescription is for the purpose of describing the particular versions orembodiments only, and is not intended to limit the scope.

In the above detailed description, reference is made to the accompanyingdrawings, which form a part hereof. In the drawings, similar symbolstypically identify similar components, unless context dictatesotherwise. The illustrative embodiments described in the detaileddescription, drawings, and claims are not meant to be limiting. Otherembodiments may be used, and other changes may be made, withoutdeparting from the spirit or scope of the subject matter presentedherein. It will be readily understood that the aspects of the presentdisclosure, as generally described herein, and illustrated in theFigures, can be arranged, substituted, combined, separated, and designedin a wide variety of different configurations, all of which areexplicitly contemplated herein.

The present disclosure is not to be limited in terms of the particularembodiments described in this application, which are intended asillustrations of various aspects. Many modifications and variations canbe made without departing from its spirit and scope, as will be apparentto those skilled in the art. Functionally equivalent methods andapparatuses within the scope of the disclosure, in addition to thoseenumerated herein, will be apparent to those skilled in the art from theforegoing descriptions. Such modifications and variations are intendedto fall within the scope of the appended claims. The present disclosureis to be limited only by the terms of the appended claims, along withthe full scope of equivalents to which such claims are entitled. It isto be understood that this disclosure is not limited to particularmethods, reagents, compounds, compositions or biological systems, whichcan, of course, vary. It is also to be understood that the terminologyused herein is for the purpose of describing particular embodimentsonly, and is not intended to be limiting.

As used in this document, the singular forms “a,” “an,” and “the”include plural references unless the context clearly dictates otherwise.Unless defined otherwise, all technical and scientific terms used hereinhave the same meanings as commonly understood by one of ordinary skillin the art. Nothing in this disclosure is to be construed as anadmission that the embodiments described in this disclosure are notentitled to antedate such disclosure by virtue of prior invention. Asused in this document, the term “comprising” means “including, but notlimited to.”

While various compositions, methods, and devices are described in termsof “comprising” various components or steps (interpreted as meaning“including, but not limited to”), the compositions, methods, and devicescan also “consist essentially of” or “consist of” the various componentsand steps, and such terminology should be interpreted as definingessentially closed-member groups.

With respect to the use of substantially any plural and/or singularterms herein, those having skill in the art can translate from theplural to the singular and/or from the singular to the plural as isappropriate to the context and/or application. The varioussingular/plural permutations may be expressly set forth herein for sakeof clarity.

It will be understood by those within the art that, in general, termsused herein, and especially in the appended claims (e.g., bodies of theappended claims) are generally intended as “open” terms (e.g., the term“including” should be interpreted as “including but not limited to,” theterm “having” should be interpreted as “having at least,” the term“includes” should be interpreted as “includes but is not limited to,”etc.). It will be further understood by those within the art that if aspecific number of an introduced claim recitation is intended, such anintent will be explicitly recited in the claim, and in the absence ofsuch recitation no such intent is present. For example, as an aid tounderstanding, the following appended claims may contain usage of theintroductory phrases “at least one” and “one or more” to introduce claimrecitations. However, the use of such phrases should not be construed toimply that the introduction of a claim recitation by the indefinitearticles “a” or “an” limits any particular claim containing suchintroduced claim recitation to embodiments containing only one suchrecitation, even when the same claim includes the introductory phrases“one or more” or “at least one” and indefinite articles such as “a” or“an” (e.g., “a” and/or “an” should be interpreted to mean “at least one”or “one or more”); the same holds true for the use of definite articlesused to introduce claim recitations. In addition, even if a specificnumber of an introduced claim recitation is explicitly recited, thoseskilled in the art will recognize that such recitation should beinterpreted to mean at least the recited number (e.g., the barerecitation of “two recitations,” without other modifiers, means at leasttwo recitations, or two or more recitations). Furthermore, in thoseinstances where a convention analogous to “at least one of A, B, and C,etc.” is used, in general such a construction is intended in the senseone having skill in the art would understand the convention (e.g., “asystem having at least one of A, B, and C” would include but not belimited to systems that have A alone, B alone, C alone, A and Btogether, A and C together, B and C together, and/or A, B, and Ctogether, etc.). In those instances where a convention analogous to “atleast one of A, B, or C, etc.” is used, in general such a constructionis intended in the sense one having skill in the art would understandthe convention (e.g., “a system having at least one of A, B, or C” wouldinclude but not be limited to systems that have A alone, B alone, Calone, A and B together, A and C together, B and C together, and/or A,B, and C together, etc.). It will be further understood by those withinthe art that virtually any disjunctive word and/or phrase presenting twoor more alternative terms, whether in the description, claims, ordrawings, should be understood to contemplate the possibilities ofincluding one of the terms, either of the terms, or both terms. Forexample, the phrase “A or B” will be understood to include thepossibilities of “A” or “B” or “A and B.”

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, such as in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” and the like include the number recited andrefer to ranges which can be subsequently broken down into subranges asdiscussed above. Finally, as will be understood by one skilled in theart, a range includes each individual member. Thus, for example, a grouphaving 1-3 cells refers to groups having 1, 2, or 3 cells. Similarly, agroup having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells,and so forth.

Various of the above-disclosed and other features and functions, oralternatives thereof, may be combined into many other different systemsor applications. Various presently unforeseen or unanticipatedalternatives, modifications, variations or improvements therein may besubsequently made by those skilled in the art, each of which is alsointended to be encompassed by the disclosed embodiments.

Example

A novel miniature trace explosives trace preconcentrator device wasdeveloped as shown in FIG. 6. The device had the followingcharacteristics as shown in Table 2

TABLE 2 Collected media Particles, aerosol and vapors Type of substrateProprietary functional monomer on stainless steel wool Pulsed heatingInductive RF (patent pending) Preconcentration factor Up to 1000 Lowpressure drop 0.4 PSI for 0.1 g substrate Fast heating 85-125° C./secReleased vapors volume As little as 5-10 mL. Could be adjusted. Tunedaffinity to a group of Nitro-, Phosphorus-, etc. chemicals Low price forthe coated substrate <$0.15 Reusable Up to 20 times Low outgassing Up to275° C. Excellent coating adhesion At least 20 cycles Coating thermalstability AT least 250° C. Not sensitive to a thermal shock Tested at150° C./sec Low mass media 0.1 g and 0.5 g Low power consumption <50Joules for heating 0.1 g substrate to 250° C. COTS detectors tested withIMS, DMS and MS pre-concentrator Selectivity improvement in 2^(nd) handsmoke, gasoline exhaust presence of Device Size 3.2″ × 1.7″ × 4.3″Pre-concentrator tube ID 0.2″ Weight with a battery 312 g (11 oz)Battery Lithium-Polymer Battery (11.1 V, 325 mAh) Number of heatingcycles on Up to 200 a battery

To measure quantitative preconcentration efficiency, the preconcentratorwas interfaced with a quadruple mass spectrometer (MS). Experimentalresults (FIGS. 9 and 10) show repeatable TNT vapor pre-concentration. Itshould be noted that preconcentration efficiency will depend on the typeof explosive and analyte vapor pressure.

Preconcentrator performance also was tested with COTS trace detector,QS-150, manufactured by Implant Sciences Corp. 0.5 g of DNT was placedinto 50 ml syringe. Syringe pump was used to control sample air-flow andreleased vapors air-flow. Total time of vapor sampling and analysis foreach set of experiment was 15 sec. Each curve on FIGS. 11-14 correspondsto 1 sec of sampling/analysis. All spectra are shown only for 29-40 msregion. Reactive ion peak (RIP) maximum amplitude was close to 3000counts.

FIG. 11 shows IMS spectra of laboratory air. FIG. 12 shows IMS spectrarelated to DNT vapors injected from a syringe into ETD. The spectra weretaken with interval of 1 sec. When preconcentrator was placed betweenthe syringe with DNT vapors and IMS detector sampling port, DNT vaporscould not reach the detector (see FIG. 13). After DNT vapor sampling thepre-concentrator with collected DNT vapors was heated within 1.8 sec andreleased vapors were injected into the detector. In a set of experimentswe varied air-flow of released DNT vapors. FIG. 14 shows IMS detectorresponse to released DNT vapors released with various flow rates of 50,75, 100 and 120 ml/min.

What is claimed is:
 1. A preconcentrator comprising: a cartridge; and acoated substrate having a resistivity of about 10⁵ ohm-meters (Ω·m) toabout 10⁻⁷ Ω·m and magnetic permeability of greater than about 1×10⁻⁴H/m enclosed within the cartridge; and wherein the coated substratecomprises polymer having a backbone containing benzene, toluene, xylene,cyclohexane, dimethylcyclohexane, ethylcyclohexane, or combinationsthereof.
 2. The preconcentrator of claim 1, wherein the substrate isselected from the group consisting of metal fiber, woven metal fibers,non-woven metal fibers, porous metal, sheet metal, metal coated glass,metal coated plastic, metal coated ceramic, carbonaceous material,graphite, charcoal, activated carbon, activated carbon cloth, andcombinations thereof.
 3. The preconcentrator of claim 1, wherein thesubstrate relative permeability of greater than
 100. 4. Thepreconcentrator of claim 1, wherein the substrate has an electricalresistivity of greater than 10³ Ω·m.
 5. The preconcentrator of claim 1,wherein the cartridge further comprises at least a first reversiblysealable opening on one side of the cartridge and at least a secondreversibly sealable opening on the opposite side of the cartridge.
 6. Amethod for detecting a chemical comprising: collecting particles andgases in a preconcentrator comprising a cartridge and a coated substrateenclosed in a cartridge, the substrate having a resistivity of about 10⁵ohm-meters (Ω·m) to about 10⁻⁷ Ω·m and magnetic permeability of greaterthan about 1×10⁻⁴ H/m; heating the substrate to release the particlesand gases; and detecting the chemical, wherein the coated substratecomprises polymer having a backbone containing benzene, toluene, xylene,cyclohexane, dimethylcyclohexane, ethylcyclohexane, or combinationsthereof.
 7. The method of claim 6, wherein the substrate relativepermeability of greater than
 100. 8. The method of claim 6, whereinheating is carried out to about 200° C. to about 350° C.
 9. The methodof claim 6, wherein the heating is inductive heating.
 10. The method ofclaim 9, wherein inductive heater is carried out at a frequency of about100 kHz to about 10 MHz.
 11. A sample collector comprising: apreconcentrator comprising a coated substrate having a resistivity ofabout 10⁵ ohm-meters (Ω·m) to about 10⁻⁷ Ω·m and magnetic permeabilityof greater than about 1×10⁻⁴ H/m; a sample collector housing having apreconcentrator holder sized to reversibly receive the preconcentrator;and an air suction pump operably connected to the sample collectorhousing and configured to produce air flow through the preconcentrator,wherein the coated substrate comprises polymer having a backbonecontaining benzene, toluene, xylene, cyclohexane, dimethylcyclohexane,ethylcyclohexane, or combinations thereof.
 12. The sample collector ofclaim 11, further comprising a pulsed air nozzle connected to the samplecollector housing.
 13. The sample collector of claim 11, furthercomprising an air compressor operably connected to the sample collectorhousing and is configured to expel air from the pulsed air nozzle anddirect the expelled air toward a sample collection area.
 14. The samplecollector of claim 11, wherein the air suction pump provides a flow of 1m³/min to 10 m³/min.
 15. A system comprising: a sample collectorcomprising: a preconcentrator comprising a coated substrate having aresistivity of about 10⁵ ohm-meters (Ω·m) to about 10⁻⁷ Ω·m and magneticpermeability of greater than about 1×10⁻⁴ H/m; a sample collectorhousing having a preconcentrator holder sized to reversibly receive thepreconcentrator; a detector comprising: a detector housing having adetector access port sized to reversibly receive the preconcentrator; aninduction heater contained within the detector housing, the inductionheater configured to heat the preconcentrator; and a sensing systemconnected to the access port and positioned to receive desorbed gasesfrom the preconcentrator when the preconcentrator is received by thedetector, wherein the coated substrate comprises polymer having abackbone containing benzene, toluene, xylene, cyclohexane,dimethylcyclohexane, ethylcyclohexane, or combinations thereof.
 16. Thesystem of claim 15, further comprising an air suction pump operablyconnected to the sample collection housing and configured to produce airflow through the preconcentrator.
 17. The system of claim 16, whereinthe air suction pump provides a flow of 1 m³/min to 10 m³/min.
 18. Thesystem of claim 15, wherein the sample collector further comprises apulsed air nozzle connected to the sample collector housing.
 19. Thesystem of claim 18, further comprising an air compressor operablyconnected to the sample collector housing and configured to expel airfrom the pulsed air nozzle and direct the expelled air toward a samplecollection area.
 20. The system of claim 15, wherein preconcentratorcomprises a cartridge and a substrate having a resistivity of about 10⁵ohm-meters (Ω·m) to about 10⁻⁷ Ω·m enclosed within the cartridge. 21.The system of claim 15, wherein the detector comprises a temperaturefeedback that limits the temperature to about 200° C. to about 350° C.22. The system of claim 15, wherein the detector further comprises acompressor operably connected to the detector access port and configuredto generate a differential pressure across the preconcentrator when thepreconcentrator is received by the detector.
 23. The preconcentrator ofclaim 1, wherein the coated substrate comprises coating having polarfunctional groups selected from the group consisting of amide(—C(O)NH₂), C₁-C₁₀ alkyl amide, carboxylic acid (—COOH), C₁-C₁₀ alkylcarboxylic acid, hydroxyl (—OH), C₁-C₁₀ alkyl hydroxyl, C₁-C₁₀ alkyoxy,aldehyde (—C(O)H), C₁-C₁₀ alkyl aldehyde, ketone (—C(O)CH₃), C₁-C₁₀alkyl ketone, amine (—NH₂), C₁-C₁₀ alkyl amine, epoxide, and carbonylgroup.
 24. The preconcentrator of claim 1, wherein the coated substratecomprises coating having non-polar functional groups selected from thegroup consisting of C₁-C₁₀ alkyl, C₂-C₁₀ alkene, C₂-C₁₀ alkyne, C₆-C₁₆arene, halide (Br, F, Cl), C₁-C₁₀ alkyl halide, and cycloalkyl.
 25. Thepreconcentrator of claim 1, wherein the coated substrate comprisescoating that is a copolymer of 4-hydroxy[2.2]paracyclophane and4-perfluoro-alkylcarbonly[2.2]paracyclophane.
 26. The preconcentrator ofclaim 6, wherein the coated substrate comprises coating having polarfunctional groups selected from the group consisting of amide(—C(O)NH₂), C₁-C₁₀ alkyl amide, carboxylic acid (—COOH), C₁-C₁₀ alkylcarboxylic acid, hydroxyl (—OH), C₁-C₁₀ alkyl hydroxyl, C₁-C₁₀ alkyoxy,aldehyde (—C(O)H), C₁-C₁₀ alkyl aldehyde, ketone (—C(O)CH₃), C₁-C₁₀alkyl ketone, amine (—NH₂), C₁-C₁₀ alkyl amine, epoxide, and carbonylgroup.
 27. The preconcentrator of claim 6, wherein the coated substratecomprises coating having non-polar functional groups selected from thegroup consisting of C₁-C₁₀ alkyl, C₂-C₁₀ alkene, C₂-C₁₀ alkyne, C₆-C₁₆arene, halide (Br, F, Cl), C₁-C₁₀ alkyl halide, and cycloalkyl.
 28. Thepreconcentrator of claim 6, wherein the coated substrate comprisescoating that is a copolymer of 4-hydroxy[2.2]paracyclophane and4-perfluoro-alkylcarbonly[2.2]paracyclophane.
 29. The preconcentrator ofclaim 11, wherein the coated substrate comprises coating having polarfunctional groups selected from the group consisting of amide(—C(O)NH₂), C₁-C₁₀ alkyl amide, carboxylic acid (—COOH), C₁-C₁₀ alkylcarboxylic acid, hydroxyl (—OH), C₁-C₁₀ alkyl hydroxyl, C₁-C₁₀ alkyoxy,aldehyde (—C(O)H), C₁-C₁₀ alkyl aldehyde, ketone (—C(O)CH₃), C₁-C₁₀alkyl ketone, amine (—NH₂), C₁-C₁₀ alkyl amine, epoxide, and carbonylgroup.
 30. The preconcentrator of claim 11, wherein the coated substratecomprises coating having non-polar functional groups selected from thegroup consisting of C₁-C₁₀ alkyl, C₂-C₁₀ alkene, C₂-C₁₀ alkyne, C₆-C₁₆arene, halide (Br, F, Cl), C₁-C₁₀ alkyl halide, and cycloalkyl.
 31. Thepreconcentrator of claim 11, wherein the coated substrate comprisescoating that is a copolymer of 4-hydroxy[2.2]paracyclophane and4-perfluoro-alkylcarbonly[2.2]paracyclophane.
 32. The preconcentrator ofclaim 15, wherein the coated substrate comprises coating having polarfunctional groups selected from the group consisting of amide(—C(O)NH₂), C₁-C₁₀ alkyl amide, carboxylic acid (—COOH), C₁-C₁₀ alkylcarboxylic acid, hydroxyl (—OH), C₁-C₁₀ alkyl hydroxyl, C₁-C₁₀ alkyoxy,aldehyde (—C(O)H), C₁-C₁₀ alkyl aldehyde, ketone (—C(O)CH₃), C₁-C₁₀alkyl ketone, amine (—NH₂), C₁-C₁₀ alkyl amine, epoxide, and carbonylgroup.
 33. The preconcentrator of claim 15, wherein the coated substratecomprises coating having non-polar functional groups selected from thegroup consisting of C₁-C₁₀ alkyl, C₂-C₁₀ alkene, C₂-C₁₀ alkyne, C₆-C₁₆arene, halide (Br, F, Cl), C₁-C₁₀ alkyl halide, and cycloalkyl.
 34. Thepreconcentrator of claim 15, wherein the coated substrate comprisescoating that is a copolymer of 4-hydroxy[2.2]paracyclophane and4-perfluoro-alkylcarbonly[2.2]paracyclophane.